CA2126502C - Catalyst for reduction of carbon dioxide - Google Patents
Catalyst for reduction of carbon dioxide Download PDFInfo
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- CA2126502C CA2126502C CA002126502A CA2126502A CA2126502C CA 2126502 C CA2126502 C CA 2126502C CA 002126502 A CA002126502 A CA 002126502A CA 2126502 A CA2126502 A CA 2126502A CA 2126502 C CA2126502 C CA 2126502C
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/15—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction of organic compounds with carbon dioxide, e.g. Kolbe-Schmitt synthesis
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/60—Platinum group metals with zinc, cadmium or mercury
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
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- C—CHEMISTRY; METALLURGY
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/40—Carbon monoxide
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
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Abstract
A catalyst for the reduction of carbon dioxide which comprises at least one transition metal selected from the group consisting of Group VIII (e. g., Ni, Fe, Co, Ru, Rh) and Group VIa (e.g., Mo, W) in the Periodic Table on zinc oxide alone or a composite containing zinc oxide and at least one metal oxide of a metal selected from the group consisting of Group IIIb (e.g., Al, Ga) and Group IVa (e.g., Ti, Zr) in the Periodic Table.
Description
CAT~~LYST 1?GR REDUCTION OF CARBON DIOXIDE
~?IELD OF THE INVENTION
The present invention relates to a catalyst for the chemical reduction of carbon dioxide which can produce carbon monoxide by the reducaion of carbon dioxide using hydrogen . In particular, they present invention relates to a catalyst for the reduction of carbon dioxide which can be suitably applied even when, as a raw material gas, a sulfur compound, such as HZS
and/or a large amount of carbon monoxide, is present in a raw material system.
BACKGROUND OF THE INVENTION
The hydrogenation reaction of carbon dioxide by hydrogen has been known and industrialized as a method for the production of a. hydrocarbon using a precious metal (e.g., Ru, Rh) type catalyst o:r a Ni type catalyst, as shown in the following reaction formula. According to this reaction, methane can be readily produced with high selectivity, and it hardly produces C0.
CC~2 + 4H2 ~ CH4 ~+ 2H20 On the other lhand, carbon monoxide alone or mixed with hydrogen in an ~equimolar amount (called oxo gas) is useful as a raw material j:or methanol synthesis, acrylic acid synthesis, formic acid synthesp~s, fatty acid synthesis, acetic acid synthesis, oxo synthesis (hydroformylation), and carbonyl synthesis, etc.
In general, carbon monoxide is produced by the steam reforming procE~ss of a light hydrocarbon.
In the steam reforming process, a light hydrocarbon ( a . g . , methane ) , watE~r and carbon dioxide are reacted in the presence of a catalyst to change the reactants to a gas containing HZ/C02/C0, then COZ in t:he gas is absorbed by an amine solution and the like, whereby a mixed gas of H2 with CO
is obtained, or which may be further deeply cooled to separate C0.
Recently, in the production of carbon monoxide, research has become active to solidify and utilize COZ as resources in view of global environmental protection. For this purpose, research has been conducted to develop a catalyst which is capable of producing CO with high selectivity by the reduction of caobon dioxide as a raw material using hydrogen, as shown in the following reaction formula.
COZ + HZ ~ CO + HZO
This reaction is to selectively produce CO without forming a hydrocarbon .
A catalyst used in this reaction is required to have a degree of conversion t~o the equilibrium degree of conversion as its activity arid high selectivity, so such a catalyst is severely difficult to design. Accordingly, if any sulfur compound such as HZS i;s in a raw material gas, the catalyst is poisoned instantly with a sulfur compound.
~?IELD OF THE INVENTION
The present invention relates to a catalyst for the chemical reduction of carbon dioxide which can produce carbon monoxide by the reducaion of carbon dioxide using hydrogen . In particular, they present invention relates to a catalyst for the reduction of carbon dioxide which can be suitably applied even when, as a raw material gas, a sulfur compound, such as HZS
and/or a large amount of carbon monoxide, is present in a raw material system.
BACKGROUND OF THE INVENTION
The hydrogenation reaction of carbon dioxide by hydrogen has been known and industrialized as a method for the production of a. hydrocarbon using a precious metal (e.g., Ru, Rh) type catalyst o:r a Ni type catalyst, as shown in the following reaction formula. According to this reaction, methane can be readily produced with high selectivity, and it hardly produces C0.
CC~2 + 4H2 ~ CH4 ~+ 2H20 On the other lhand, carbon monoxide alone or mixed with hydrogen in an ~equimolar amount (called oxo gas) is useful as a raw material j:or methanol synthesis, acrylic acid synthesis, formic acid synthesp~s, fatty acid synthesis, acetic acid synthesis, oxo synthesis (hydroformylation), and carbonyl synthesis, etc.
In general, carbon monoxide is produced by the steam reforming procE~ss of a light hydrocarbon.
In the steam reforming process, a light hydrocarbon ( a . g . , methane ) , watE~r and carbon dioxide are reacted in the presence of a catalyst to change the reactants to a gas containing HZ/C02/C0, then COZ in t:he gas is absorbed by an amine solution and the like, whereby a mixed gas of H2 with CO
is obtained, or which may be further deeply cooled to separate C0.
Recently, in the production of carbon monoxide, research has become active to solidify and utilize COZ as resources in view of global environmental protection. For this purpose, research has been conducted to develop a catalyst which is capable of producing CO with high selectivity by the reduction of caobon dioxide as a raw material using hydrogen, as shown in the following reaction formula.
COZ + HZ ~ CO + HZO
This reaction is to selectively produce CO without forming a hydrocarbon .
A catalyst used in this reaction is required to have a degree of conversion t~o the equilibrium degree of conversion as its activity arid high selectivity, so such a catalyst is severely difficult to design. Accordingly, if any sulfur compound such as HZS i;s in a raw material gas, the catalyst is poisoned instantly with a sulfur compound.
As an improved catalyst for this purpose, JP-A-4-363142 discloses a tungsten sulfide catalyst and a molybdenum sulfide catalyst. (The term ",:fP-A" as used herein means an "unexamined published Japanese patent application".) These catalysts are prepared by previously treating ammonium tetrathiotungstate [ { NH4 ) zWS4 ] or ammonium tetrathiomolybd.ate [(NH4)ZMoS4] under HZ stream at 300 to 400°C
to prepare WSZ or MaS2.
Also, there a.re catalysts such as MoSZ/Ti02, MoSZ/A1203 which are prepared by dipping a carrier such as Ti02, A1203, Si02 in the above-mentioned aqueous ammonium sulfide solution to which an aqueous ammonia is added for support, followed by drying and pretreatmenlt.
These catalysts are not poisoned with a sulfur compound, since a metal sulfide is used as a catalyst active component.
Moreoveo, it is known that these catalysts are capable of producing CO in tike reduction reaction of carbon dioxide using a mixed c~as of carbon dioxide and hydrogen with high selectivity without foz-ming a hydrocarbon.
Furthermore, wince these catalysts do not suffer the poisoning functp_on from a sulfur compound as discussed above, they are also advantageous in that no removal of HZS is required.
However, in cases where a large amount of CO is contained in a raw material gas, it is generally known, as 21~650~
shown in the following reaction formulas, that they remarkably form a hydrocarbon and/or deposit a carbon, further they bring about the deact_Lvatio:n of these catalysts due to C0.
CO + (m/:2n + 1 )HZ -~ 1/n x CnHm + HZO
(formation. of a hydrocarbon) 2C0 -~ CO~, + C~.
(deposit~Lon of a carbon) In addition, in cases where a slight amount of sulfur compound is contained or no sulfur compound is contained in a raw material g,as, a metal sulfide as a catalyst active component is reduced with hydrogen to form HzS in the reaction of carbon dioxide with hydrogen, then the HZS is transferred to a reaction product in the COZ-HZ system, and, as a result, the catalyst is deactivated.
Furthermore, regardless of the presence or absence of a sulfur compound, su.c:h as HZS, in a raw material gas, any post-treatment for removing HZS is required due to the transferred HZS :Ln the reaction product.
On the other hand, a reaction gas is condensed and circulated after separation of a great amount of unreacted COz in the process of forrr~i:ng an oxo gas ( CO/HZ = 1 ) by the steam reforming process and i.n the process of separating CO conducted by deeply cooling the resulting oxo gas. Accordingly, when a sulfur compound such as HZS is slipped into a formed gas in the course of the recjuction of a catalyst, the sulfur compound is condensed at the same itime in the course of COZ separation and COZ condensation steps and the condensed sulfur compound is introduced to a reforming reactor, then a reforming catalyst is unfavorably po_Lsoned, which is observed in using a sulfide catalyst. In this process, it is important to decrease an amount of unreacted C0, for cost saving. For this purpose, it is essentially required to conduct the reverse shift reaction of a reforming c~as containing CO, C02, Hz to decrease the amount of COZ in the gas. Gen<~rally, in cases where CO is present, it brings about remarkable catalyst poisoning, carbon deposition, and hydrocarbon formation, etc.
The present invention is based on the following findings which were obtained in research and development relating to a carbon dioxide reduction catalyst for obtaining carbon monoxide by the reduction of carbon dioxide with hydrogen. Specifically, in the use of a catalyst carrying a transition metal_ on a zinc oxide alone or a composite having a zinc oxide and a metal oxide selected from either Group IIIb or Group IVa or k>oth in the Periodic Table, inclusive of a catalyst which is devE~l.oped for the deep desulfurization of a middle or light distillate oil, (1) even though a sulfur compound such as HzS is present in a raw material gas, these catalysts are not poisoned with it, then the catalytic life is prolonged, and further the final product is not contaminated with H2S, thereby no HZS
removal treatment is required, and 2'12650 ~
(2) in particular, in cases where a composite of a zinc oxide, a titaniw:n oxide and an aluminum oxide is used as a carrier, even though CO is contained in an amount similar to COZ in a raw matE~rial gas, the hydrogenation reaction of COZ to CO proceeds selectively without accompanying any side reaction such as the poisoning of-_ a catalyst, the deposition of a carbon and the formation of a hydrocarbon.
Thus, the present invention has been completed.
SUMMARY OF THE INVENTION
An object of the present invention is to provide a catalyst for the reduction of carbon dioxide which is capable of selectively reducing COZ to CO by hydrogen, even when using a mixed gas of COZ arid HZ in which a great amount of CO is contained in a raw material system and which is resistant to poisoning by sulfur or sulfur compounds.
More specifical=Ly, the present invention is to provide a catalyst for the reduction of carbon dioxide characterized by carrying a transition :metal on zinc oxide alone or a composite containing zinc oxide and at least one metal oxide of a metal selected from metals in Group IIIb and Group IVa in the Periodic Table.
In a preferrec9 embodiment, the metal oxide selected from Group IIIb and Group IVa in the Periodic Table includes a metal oxide of AIL, Ga, Ti and Zr or a composite thereof. In a preferred embodiment, the transition metal includes a metal belonging to Group VIII and Group VIa in the Periodic Table, and more preferably, it includes Ni, Fe, Co, Ru, Rh, Pt, Pd, Mo and W.
The catalyst according to the present invention is used in a reaction for obtaining carbon monoxide through the reduction of carbon dioxide by hydrogen. Even when a sulfur compound such as H2S is present in a mixed gas of carbon dioxide and hydrogen, the catalyst according to the present invention can produce carbon monoxide with high selectivity and without poisoning.
In another aspect, the present invention provides a method for reducing carbon dioxide by hydrogen in the presence of a catalyst where the reaction proceeds in the absence of an accompanying hydrocarbon forming side reaction, wherein said catalyst comprises a transition metal on a carrier comprising zinc oxide alone or on a carrier comprising zinc oxide and at least one metal oxide of a metal selected from metals in Group IIIb and IVa in the Periodic Table.
In another aspect, the present invention provides a method for reducing carbon dioxide by hydrogen in the presence of a catalyst, wherein said catalyst comprises molybdenum present as oxide on a carrier comprising zinc oxide and aluminum oxide.
In another aspect, the present invention provides a method for reducing carbon dioxide by hydrogen in the presence of a catalyst, wherein said catalyst comprises nickel present as oxide on a carrier comprising zinc oxide and aluminum oxide.
BRIEF EXPLANATION OF DRAWING
The figure is a graph showing a change of the degree of COz conversion and a change of the HZS concentration in a formed gas with the Lapse of reaction time when the catalyst in Comparative Example 3 was used.
DETAILED DESCRIPTION OF THE INVENTION
In the catalyst according to the present invention, exemplary carriers include a zinc oxide alone, a zinc oxide-containing metal oxide selected from Group IIIb and Group IVa in the Periodic Table (e.g. , a metal oxide of Al, Ga, Ti, Zr) or a composite thereof (e.g. , a composite of zinc oxide, and titanium oxide, a composite of zinc oxide and aluminum oxide, a composite of zinc oxide, titanium oxide and aluminum oxide ) .
In particular, in the case using a composite of zinc oxide and titanium oxide or aluminum oxide as a carrier, the catalyst according to the present invention is hardly poisoned with a sulfur compound and CO even though a great amount of CO
- 7a -is contained a~~ well as a sulfur compound such as HZS in the above-mentioned mixed gas.
The amount of ~:inc oxide in a carrier generally ranges from about 20 to 100 wt$ based on the total amount of the catalyst in terms of the metal oxide. If the amount of zinc oxide is too small, the catalytic life is not sufficiently prolonged. Almost all the sulfur compound, such as HZS, in a raw material gas is absorbed in the zinc oxide of a carrier, whereby it is consi_d.ered that the active component is not poisoned and they cata7Lytic life is prolonged. Accordingly, in a case containing no zinc oxide, these effects cannot be obtained, which result=~ in a short catalytic life.
Furthernvore, cahen a composite is used, the mechanical strength of the catalyst is improved. In particular, in a case using a composite cont~ai_ning titanium oxide and aluminum oxide, the selectivity of carbon monoxide is improved and the resistance to CO poisoning and the resistance to coke formation are improved as compared with a case containing zinc oxide alone as demonstrated i.n the working examples of the present invention.
If these components for a carrier are to small, the resulting effects are insufficient, in contrast, if too much, the amount of a zinc oxide becomes relatively small, the HZS
absorption effeci~ decrE~ases. Accordingly, it is preferred that these components for a carrier are used in an amount from about _ g _ 21,6502 40 to 80 wt~ bas;ed on the total amount of the catalyst in terms of the metal oxide.
In cases where titanium oxide and aluminum oxide are used together, their mixing ratio is not limited, and it is acceptable that the total amount thereof is from about 40 to 80 wt~ based on them total amount of the catalyst in terms of the metal oxide.
Any transition. metal may be used as an active component. In particular, it is preferred to use a metal belonging to Group VI7:I in the Periodic Table (especially, Ni, Fe, Co, Ru, Rh, Pt, Pd) or a metal belonging to Group VIa in the Periodic Table (especially, Mo, W). These transition metals may be u:>ed alone or in a mixture of two or more.
The carrying amount of a transition metal (when two or more are used in a mixture, it is the total amount thereof) is not limited, bui~ it generally ranges from about 5 to 20 wt~
based on the total amount of the catalyst in terms of the metal oxide.
If the amount of the transition metal is too small, it is insufficient: to produce carbon monoxide with high selectivity in t:he reduction of carbon dioxide by hydrogen and insufficient to make a~ sulfur compound, such as HZS, in a raw material gas which is capable of easily absorbing to zinc oxide. If too much, these effects are saturated, thus there is no technical significance and rather it is uneconomical.
_ g _ For instance, the catalyst according to the present invention is obtained. by i) preparing a carrier using a zinc compound alone or a zinc compound and either one or both of an aluminum compound and/or a titanium compound, i.e., a metal oxide selected from Group IIIb or Group IVa, ii) then, according to a usual manner, impregnating a transition metal to the resulting carrier, followed by drying and calcining.
A zinc compound. and a metal oxide selected from Group III are used in the form of a hydroxide, a chloride, an oxide, and the like of the sE~lected element to be used.
A transition metal is used in the form of a hydroxide, a nitrate, an acetate, a chloride, and the like of the transition metal..
In cases where zinc oxide is used alone as a carrier, it is prepared, for E~x:arnple, by calcining metal zinc or by heat-decomposing an inorganic zinc salt (e. g., zinc nitrate, basic zinc carbonate) or an organic zinc (e. g., zinc benzoate, zinc citrate, zinc lactate).
In cases of a composite of zinc oxide and a metal oxide selected from either c.;roup IIIb or Group IVa or both, it is prepared, for a}:ample,, by mixing a titanium hydroxide or an aluminum hydroxide or .a mixture thereof with a zinc hydroxide, or by adding alkali to a titanium compound or an aluminum compound other than th~~ hydroxide or a mixture thereof for co-precipitation, f~ollowE~d by washing, molding and calcining, according to a u;~ual manner.
In a composite of a zinc oxide and a metal oxide selected from Either croup IIIb o~_- Group IVa or both, the mixing order of each components (inc:lusive of a hydroxide) is not limited. For instance, it may be prepared by mixing a mixture of a titanium compound and an aluminum compound with a zinc compound as described above, or by mixing a mixture of either a titaniiun comloound or an aluminum compound and a zinc compound with tree other non-mixed compound thereof.
Otherwise, a carrier having desired properties for the catalyst according to tile present invention may be prepared by only mixing a powder of a zinc oxide, a titanium oxide, an aluminum oxide, etc. i.n a prescribed amount.
A transition mf=t.al may be carr_.ied on the above-prepared carrier according to a conventional method such as an impregnation method and a co-precipitation method.
As an example, in a case carrying Ni as a transition metal on a carrier made of a zinc oxide alone, water is gradually added dropwise to a zinc oxide for water absorbing at the inside of the= zinc oxide. It is preferred that the water absorbing is concjucted until it is saturated at the inside of the zinc oxide. Next, the necessary Ni amount is calculated by the saturated water absorbing amount and the zinc oxide amount.
then, an aqueous Ni salt (e.g., a nitrate, an acetate, a chloride) solution which has been adjusted to an appropriate concentration based on the calculated Ni amount, is absorbed in 2'1 2'650 2 the zinc oxide until it is saturated, followed by washing, drying, molding, and c~alcining.
It is :similar in cases where two or more transition metals are carried on a composite as carrier. For instance, i) water is absorbed at the inside of the composite (preferably until it is sa.turated), ii) the necessary transition metal amounts (the i~otal amount of two transition metals) are calculated by the saturated water absorbing amount and the zinc oxide amount in the composite, iii) an aqueous transition metals solution which has been adjusted to an appropriate concentration based on the calculated transition metals amount, is absorbed until it i.s saturated, followed by washing, etc. as mentioned above.
When the catalyst according to the present invention is used to obtain carbon monoxide in the reduction of carbon dioxide by hydrogen, a suitable carbon monoxide production can be achieved, even though a sulfur compound, such as HZS, is present in a raw material gas, or, in a case using a composite of zinc oxide, titanium oxide, and aluminum oxide as a carrier, a great amount of CO i~~ present in the raw material gas.
In the reaction using a catalyst according to the present invention, it is preferred to be conducted at a temperature of about 400°C or more, more preferably at about 500 to 600°C under a pressure of about 20 kg/cmz or less, more preferably atmospheric: pressure to about 5 kg/cmz, and GHSV of about 1000 to 30000 h-1.
As discussed above, the catalyst according to the present invention carp provide the following effects:
(1) Even though a sulfur compound, such as HZS, is present in a raw material gas for obtaining carbon monoxide by reduction reaction of carbon dioxide by hydrogen, the catalyst according to the pre:~ent invention is not poisoned, then the catalytic life is prolonged.
(2) Since them final product obtained by the reduction reaction is not contaminated with HZS by the reduction of the catalyst, no HZ~~ removal treatment is required.
(3) In particular, in cases where a composite of zinc oxide, titanium oxide and aluminum oxide is used as a carrier, even though CO is contained in an amount similar to COZ in a raw material gas, them reduction reaction proceeds favorably with improved selectivity without accompanying any side reaction such as the poisoning of a catalyst, the deposition of carbon and the formation of a light hydrocarbon.
(4) Accordingly, by conducting the above-mentioned reduction reaction, carbon monoxide can be produced with a high degree of conversion and high selectivity. .
The catalyst according to the present invention is of great industrial value for obtaining an oxo gas and the like.
The present invE~ntion will be further described in the following examples, but. the present invention should not be construed as being limited thereto.
In the :following examples, each reaction product (gas) was analyzed by means of a gas chromatography equipped with a thermal conductive detector (TCD), by charging 60/80 mesh of an active carbon i~o a column (made of SUS) having I.D. (Inner Diameter) of 3 mm~ y: 2 m. HZS was detected by a gas indicator tube (Kitagawa type).
20 g of a carrier obtained b;y mixing 9.8 g of titanium oxide powder, 5.7 g o:E zinc oxide powder and 4.5 g of aluminum oxide powder was dipped in an aqueous solution of 9.91 g of nickel ( I I ) nitra to hexahydrate [ Ni ( NU3 ) Z ~ 6H20 ] in 20 ml of water for 1 hour. After removal of the residual solution, the resulting product was dried at 120°C for 12 hours and calcined at 600°C for 3 hours. Then, a catalyst having NiO: 12.4 wt$, ZnO: 21.2 wt~, and balance: TiOz and A1z03 was obtained.
8 ml of the catalyst thus obtained was charged in a cylindrical reaction tube having an inner diameter of 16 mm~
and 50 ml/min of HZ was passed thereto under normal pressure at 350°C for 6 hours.
Thereafter, using the catalyst, a reduction reaction of COZ by HZ was conducted with a mixed gas of Hz:COz ( 1 : 1 ) as a raw material gas under normal pressure at 600°C and GHSV = 3000h''.
The resu~~ts are shown in Table 1.
20 g of a carrier which was prepared in the same manner as in Example 1 was dipped in an aqueous solution of 9.88 g of 2~ 2650 2 cobalt ( I I ) nitrate hE~xahydrate [ Co ( N03 ) 2 ~ 6H20 ] dissolved in 20 ml of water. After removal of the residual solution, the resulting product was dried at 120°C' for 12 hours and calcined at 600°C for 3 ihours. Then, a catalyst having CoO: 12.7 wt~, Zn0:21.5 wt$, and balance: TiOz and A1203 was obtained.
Using the catalyst thus obtained, a reduction reaction was conducted in the name manner as in Example 1.
The results are shown in Table 1.
In an aqueous anunonium para-molybdate solution in which . 2 g of ammonium para-~molybdate tetrahydrate [ ( NH4 ) 6MO~OZ4 ~ 4Hz0 ]
was dissolved i.n 20 ml of water and aqueous ammonia was dropwise added thereto was dipped 20 g of a carrier which was prepared in the ;same manner as in Example 1 for 1 hour. After removal of the :residual solution, the resulting product was dried at 120°C to 12 hours and calcined at 600°C for 3 hours.
Then, a catalyst havi.n.g Mo03: 15 wt$, ZnO: 21.3 wt~, balance:
Ti02 and A1203 wa:~ obta.ined.
Using the catalyst thus obtained, a reduction reaction was conducted in the same manner as in Example 1.
The results arE~ shown in Table 1.
A catalyst having NiO: 19.1 wt$, ZnO: 70.0 wt~ was prepared in the same manner as in Example 1, except that 20 g of a carrier made of zin<~ oxide alone (a molded product of "G-72" produced by Girdles Co.) and an aqueous solution of 19.86 g of nickel ( I I ) nitrate hexahydrate [ Ni ( N03 ) Z ~ 6H20 ) dissolved in 20 ml of water were u.s~~d.
Using tlZe catalyst thus obtained, a reduction reaction was conducted in the same manner as in Example 1.
The results arE~ shown in Table 1.
A catalyst having NiO: 12.4 wt~ and balance: TiOz and A1203 was prepared in the same manner as in Example 1, except that 20 g of a carrier made from a mixture of 10 g of titanium oxide powder and 10 g of aluminum oxide powder was used.
Using the catalyst thus obtained, a reduction reaction was conducted in the same manner as in Example 1.
The results a:re shown in Table 1.
Ex.l Ex. 2 Ex. 3 Ex. 4 Comp. Ex. 1 Formed Gas Composition:
(Vol$) Hz 40.4 41.3 41.9 37.5 41.0 CO 21.0 20.2 18.5 22.0 20.8 COZ 38.5 38.4 39.6 39.3 38.1 CH4 0.1 0.1 0.0 1.2 0.1 Degree of Conversion: 35.0 34.0 32.0 36.6 34.9 ($) Selectivity: 99.5 99.5 100 94.8 99.5 ( Equilibrium Degree of Conversion: 385 38.5 38.5 38.5 38.5 ( In the results of Table 1, the degree of conversion and the selectivity are calculated by the following two equations, and the equilibrium degree of conversion means a theoretical degree of conversion.
(C'.Oz Mol. Number in .- (C02 Mol. Number Degree of Raw Material Gas) in Formed Gas) Conversion = ____._____.___________________________________ x 100 C0.> M~~1. Number in Raw Material Gas (CO Mol. Number - (CO Mol. Number in in Formed Gas) Raw Material Gas) Selectivity = _________.__________________________________x 100 ( ~ ) ( c~02 Mol . Number in _ ( C02 Mol . Number Raw Material Gas) in Formed Gas) A reduction rea~~tion was conducted in the same manner as in Example 1, except that a catalyst prepared in the same manner as in Example 4 was used and a mixed gas of Hz:COz (1:1) containing 200 p:pm of H;S was used as a raw material gas.
The resu:Lts are shown in Table 2.
Reaction Time 50 Hr 100 Hr 150 Hr Formed Gas Composition (Volt):
HZ 37.4 37.5 37.5 CO 21.9 22.0 22.0 COZ 39.5 39.5 39.5 CH4 1.2 1.1 1.1 Degree of Conver:;ion ( '~ ) : 36 . 5 36 . 5 36 . 5 Selectivity (~): 94.8 95.2 95.2 Outlet HZS Concentration (ppm): 0 0 0 2'1 2650 2 C:OMPARATIVE EXAMPLE 2 A reduction reaction was conducted in the same manner as in Example J., exc<~pt for using a catalyst prepared in the same manner a~~ in Comparative Example 1 and a mixed gas prepared in the same manner as in Example 5.
The results are shown in Table 3.
Reaction Time 50 Hr 100 Hr 150 Hr Formed Gas Composition (Vol$):
HZ 47,1 48.4 49.3 CO 8.5 3.7 0.8 COZ 44.4 47.9 49.9 CH4 0.0 0.0 0.0 Degree of Conversion (~~): 16.0 7.1 1.5 Selectivity ($). 100 100 100 Outlet HZS Concentration (ppm): 18 92 183 The results of Tables 1 to 3 support the following:
regardless of the presence of zinc oxide in a carrier of a catalyst, when a sulfur compound such as HzS was not present in a raw material c~as, a high degree of conversion was achieved.
However, when a sulfur ~~ompound, such as HZS, was present in a raw material gas, in cares using a catalyst containing no zinc oxide in a carrier, HZS~ was passed into a formed gas or the catalyst was poisoned. with a sulfur compound such as HZS, whereby the de~~ree of conversion was decreased and the catalytic life was shortened.
~1 2s5o 2 In cases using the catalysts according to the present invention, no HZS was ~~bserved in a formed gas and, since the catalytic life Haas prolonged, the catalysts were not poisoned.
C'.O.MPARATIVE EXAMPLE 3 8 ml of a comanercially available molybdenum disulfide was charged to a cylindrical reaction tube having an inner diameter of 16 mm~. LJsing this, a reduction reaction of COZ by HZ was conducted with a mixed gas of HZ:COZ (1:1) under normal pressure at 600°C and GHSV = 3000h-1. Then, a change of the degree of conversion and a change o:f the HZS concentration in a formed gas with the lapse of a reaction time were determined.
From the figure, it is apparent that when a metal sulfide is used as a catalyst, a sulfide as a catalytic component is reduced by hydrogen to form HZS even though no sulfur compound, such as HZS, is present in a raw material gas, the formed HZS is transferred to a formed gas, whereby the catalytic activity is decreased.
Using the catalyst prepared in the same manner as in Example 1, a reduction of COZ was conducted continuously in the same manner as in Example 1, except that a mixed gas of HZ
( 49 . 7 volt ) , CO ( 28 . 4 volt ) , COZ ( 21 . 8 volt ) and CH4 ( 0. 1 volt ) containing 200 ppm of HZS was used as a raw material gas.
The results with the lapse of 24 hours and the lapse of 200 hours are shown in.'rable 4.
20 g of a carrier which was prepared in the same manner as in Example 1 was dipped in an aqueous solution of 26.15 g of iron ( I I I ) nitrate nonahydrate [ Fe ( N03 ) 3 ~ 9H20 ] dissolved in 20 ml of water for 1 hour. after removal of the residual solution, the resulting product was dried at 120°C for 12 hours and calcined at 600°C for :3 hours. Then, a catalyst having Fe203:
20.5 wt~, ZnO: 21.2 wt~, and balance: Ti02 and A1203 was obtained.
Using the catalyst thus obtained, a reduction reaction was conducted in the same manner as in Example 6.
The resL~lts with the lapse of 24 hours and the lapse of 200 hours are shown in Table 4.
A reduction reaction was conducted in the same manner as in Example 6, except for using the catalyst which was prepared in the same rnanner as in Example 3.
The results with the lapse of 24 hours and the lapse of 200 hours are shown in Table 4.
TABLE
Example Examp le Examp le Reaction Time: 24 200 24 200 24 200 (Hr) Formed Gas Composition:
(Vol$) HZ 45.'7 46.0 46.1 46.5 44.8 44.7 CO 36.'7 35.7 36.4 35.1 37.1 37.2 COZ 17.:3 17.9 17.3 18.1 17.9 17.9 CH4 0.:3 0.4 0.2 0.3 0.2 0.2 Degree of Conversion: 27.2 24.5 26.9 23.4 25.8 26.0 ( Selectivity: 94.4 88.9 93.2 85.1 97.0 96.7 ($) C-Balance: 99.7 99.3 99.4 98.8 99.8 99.8 ( In Tab_Le 4, the degree of conversion and the selectivity were calculated by the same equations described earlier in Table 1. 'rhe C-balance is a mass balance of a raw material system and a formed material system, and the lower C-balance means the deposition of carbon on a catalyst.
As is apparent: from Table 4, in cases using a catalyst according to the present: invention, especially a catalyst using a composite of a. zinc oxide, a titanium oxide and an aluminum oxide as a carrier, even though a great amount of CO is present in a raw material ga:>, the degree of conversion and the selectivity are not decreased with the lapse of time, and the 2~1 2650 2 catalyst is not: poisoned with CO in the raw material gas, or the C-balance is not decreased.
Also, it is apparent that when a great amount of CO is present in a ~~aw material gas, it is preferred to use a catalyst which carries a molybdenum oxide on such a composite.
While the invention has been described in detail and with reference to spe~~ific embodiments thereof, it will be apparent to onf~ skill in the art that various changes and modifications can be made therein without departing from the spirit and scopE= thereof.
to prepare WSZ or MaS2.
Also, there a.re catalysts such as MoSZ/Ti02, MoSZ/A1203 which are prepared by dipping a carrier such as Ti02, A1203, Si02 in the above-mentioned aqueous ammonium sulfide solution to which an aqueous ammonia is added for support, followed by drying and pretreatmenlt.
These catalysts are not poisoned with a sulfur compound, since a metal sulfide is used as a catalyst active component.
Moreoveo, it is known that these catalysts are capable of producing CO in tike reduction reaction of carbon dioxide using a mixed c~as of carbon dioxide and hydrogen with high selectivity without foz-ming a hydrocarbon.
Furthermore, wince these catalysts do not suffer the poisoning functp_on from a sulfur compound as discussed above, they are also advantageous in that no removal of HZS is required.
However, in cases where a large amount of CO is contained in a raw material gas, it is generally known, as 21~650~
shown in the following reaction formulas, that they remarkably form a hydrocarbon and/or deposit a carbon, further they bring about the deact_Lvatio:n of these catalysts due to C0.
CO + (m/:2n + 1 )HZ -~ 1/n x CnHm + HZO
(formation. of a hydrocarbon) 2C0 -~ CO~, + C~.
(deposit~Lon of a carbon) In addition, in cases where a slight amount of sulfur compound is contained or no sulfur compound is contained in a raw material g,as, a metal sulfide as a catalyst active component is reduced with hydrogen to form HzS in the reaction of carbon dioxide with hydrogen, then the HZS is transferred to a reaction product in the COZ-HZ system, and, as a result, the catalyst is deactivated.
Furthermore, regardless of the presence or absence of a sulfur compound, su.c:h as HZS, in a raw material gas, any post-treatment for removing HZS is required due to the transferred HZS :Ln the reaction product.
On the other hand, a reaction gas is condensed and circulated after separation of a great amount of unreacted COz in the process of forrr~i:ng an oxo gas ( CO/HZ = 1 ) by the steam reforming process and i.n the process of separating CO conducted by deeply cooling the resulting oxo gas. Accordingly, when a sulfur compound such as HZS is slipped into a formed gas in the course of the recjuction of a catalyst, the sulfur compound is condensed at the same itime in the course of COZ separation and COZ condensation steps and the condensed sulfur compound is introduced to a reforming reactor, then a reforming catalyst is unfavorably po_Lsoned, which is observed in using a sulfide catalyst. In this process, it is important to decrease an amount of unreacted C0, for cost saving. For this purpose, it is essentially required to conduct the reverse shift reaction of a reforming c~as containing CO, C02, Hz to decrease the amount of COZ in the gas. Gen<~rally, in cases where CO is present, it brings about remarkable catalyst poisoning, carbon deposition, and hydrocarbon formation, etc.
The present invention is based on the following findings which were obtained in research and development relating to a carbon dioxide reduction catalyst for obtaining carbon monoxide by the reduction of carbon dioxide with hydrogen. Specifically, in the use of a catalyst carrying a transition metal_ on a zinc oxide alone or a composite having a zinc oxide and a metal oxide selected from either Group IIIb or Group IVa or k>oth in the Periodic Table, inclusive of a catalyst which is devE~l.oped for the deep desulfurization of a middle or light distillate oil, (1) even though a sulfur compound such as HzS is present in a raw material gas, these catalysts are not poisoned with it, then the catalytic life is prolonged, and further the final product is not contaminated with H2S, thereby no HZS
removal treatment is required, and 2'12650 ~
(2) in particular, in cases where a composite of a zinc oxide, a titaniw:n oxide and an aluminum oxide is used as a carrier, even though CO is contained in an amount similar to COZ in a raw matE~rial gas, the hydrogenation reaction of COZ to CO proceeds selectively without accompanying any side reaction such as the poisoning of-_ a catalyst, the deposition of a carbon and the formation of a hydrocarbon.
Thus, the present invention has been completed.
SUMMARY OF THE INVENTION
An object of the present invention is to provide a catalyst for the reduction of carbon dioxide which is capable of selectively reducing COZ to CO by hydrogen, even when using a mixed gas of COZ arid HZ in which a great amount of CO is contained in a raw material system and which is resistant to poisoning by sulfur or sulfur compounds.
More specifical=Ly, the present invention is to provide a catalyst for the reduction of carbon dioxide characterized by carrying a transition :metal on zinc oxide alone or a composite containing zinc oxide and at least one metal oxide of a metal selected from metals in Group IIIb and Group IVa in the Periodic Table.
In a preferrec9 embodiment, the metal oxide selected from Group IIIb and Group IVa in the Periodic Table includes a metal oxide of AIL, Ga, Ti and Zr or a composite thereof. In a preferred embodiment, the transition metal includes a metal belonging to Group VIII and Group VIa in the Periodic Table, and more preferably, it includes Ni, Fe, Co, Ru, Rh, Pt, Pd, Mo and W.
The catalyst according to the present invention is used in a reaction for obtaining carbon monoxide through the reduction of carbon dioxide by hydrogen. Even when a sulfur compound such as H2S is present in a mixed gas of carbon dioxide and hydrogen, the catalyst according to the present invention can produce carbon monoxide with high selectivity and without poisoning.
In another aspect, the present invention provides a method for reducing carbon dioxide by hydrogen in the presence of a catalyst where the reaction proceeds in the absence of an accompanying hydrocarbon forming side reaction, wherein said catalyst comprises a transition metal on a carrier comprising zinc oxide alone or on a carrier comprising zinc oxide and at least one metal oxide of a metal selected from metals in Group IIIb and IVa in the Periodic Table.
In another aspect, the present invention provides a method for reducing carbon dioxide by hydrogen in the presence of a catalyst, wherein said catalyst comprises molybdenum present as oxide on a carrier comprising zinc oxide and aluminum oxide.
In another aspect, the present invention provides a method for reducing carbon dioxide by hydrogen in the presence of a catalyst, wherein said catalyst comprises nickel present as oxide on a carrier comprising zinc oxide and aluminum oxide.
BRIEF EXPLANATION OF DRAWING
The figure is a graph showing a change of the degree of COz conversion and a change of the HZS concentration in a formed gas with the Lapse of reaction time when the catalyst in Comparative Example 3 was used.
DETAILED DESCRIPTION OF THE INVENTION
In the catalyst according to the present invention, exemplary carriers include a zinc oxide alone, a zinc oxide-containing metal oxide selected from Group IIIb and Group IVa in the Periodic Table (e.g. , a metal oxide of Al, Ga, Ti, Zr) or a composite thereof (e.g. , a composite of zinc oxide, and titanium oxide, a composite of zinc oxide and aluminum oxide, a composite of zinc oxide, titanium oxide and aluminum oxide ) .
In particular, in the case using a composite of zinc oxide and titanium oxide or aluminum oxide as a carrier, the catalyst according to the present invention is hardly poisoned with a sulfur compound and CO even though a great amount of CO
- 7a -is contained a~~ well as a sulfur compound such as HZS in the above-mentioned mixed gas.
The amount of ~:inc oxide in a carrier generally ranges from about 20 to 100 wt$ based on the total amount of the catalyst in terms of the metal oxide. If the amount of zinc oxide is too small, the catalytic life is not sufficiently prolonged. Almost all the sulfur compound, such as HZS, in a raw material gas is absorbed in the zinc oxide of a carrier, whereby it is consi_d.ered that the active component is not poisoned and they cata7Lytic life is prolonged. Accordingly, in a case containing no zinc oxide, these effects cannot be obtained, which result=~ in a short catalytic life.
Furthernvore, cahen a composite is used, the mechanical strength of the catalyst is improved. In particular, in a case using a composite cont~ai_ning titanium oxide and aluminum oxide, the selectivity of carbon monoxide is improved and the resistance to CO poisoning and the resistance to coke formation are improved as compared with a case containing zinc oxide alone as demonstrated i.n the working examples of the present invention.
If these components for a carrier are to small, the resulting effects are insufficient, in contrast, if too much, the amount of a zinc oxide becomes relatively small, the HZS
absorption effeci~ decrE~ases. Accordingly, it is preferred that these components for a carrier are used in an amount from about _ g _ 21,6502 40 to 80 wt~ bas;ed on the total amount of the catalyst in terms of the metal oxide.
In cases where titanium oxide and aluminum oxide are used together, their mixing ratio is not limited, and it is acceptable that the total amount thereof is from about 40 to 80 wt~ based on them total amount of the catalyst in terms of the metal oxide.
Any transition. metal may be used as an active component. In particular, it is preferred to use a metal belonging to Group VI7:I in the Periodic Table (especially, Ni, Fe, Co, Ru, Rh, Pt, Pd) or a metal belonging to Group VIa in the Periodic Table (especially, Mo, W). These transition metals may be u:>ed alone or in a mixture of two or more.
The carrying amount of a transition metal (when two or more are used in a mixture, it is the total amount thereof) is not limited, bui~ it generally ranges from about 5 to 20 wt~
based on the total amount of the catalyst in terms of the metal oxide.
If the amount of the transition metal is too small, it is insufficient: to produce carbon monoxide with high selectivity in t:he reduction of carbon dioxide by hydrogen and insufficient to make a~ sulfur compound, such as HZS, in a raw material gas which is capable of easily absorbing to zinc oxide. If too much, these effects are saturated, thus there is no technical significance and rather it is uneconomical.
_ g _ For instance, the catalyst according to the present invention is obtained. by i) preparing a carrier using a zinc compound alone or a zinc compound and either one or both of an aluminum compound and/or a titanium compound, i.e., a metal oxide selected from Group IIIb or Group IVa, ii) then, according to a usual manner, impregnating a transition metal to the resulting carrier, followed by drying and calcining.
A zinc compound. and a metal oxide selected from Group III are used in the form of a hydroxide, a chloride, an oxide, and the like of the sE~lected element to be used.
A transition metal is used in the form of a hydroxide, a nitrate, an acetate, a chloride, and the like of the transition metal..
In cases where zinc oxide is used alone as a carrier, it is prepared, for E~x:arnple, by calcining metal zinc or by heat-decomposing an inorganic zinc salt (e. g., zinc nitrate, basic zinc carbonate) or an organic zinc (e. g., zinc benzoate, zinc citrate, zinc lactate).
In cases of a composite of zinc oxide and a metal oxide selected from either c.;roup IIIb or Group IVa or both, it is prepared, for a}:ample,, by mixing a titanium hydroxide or an aluminum hydroxide or .a mixture thereof with a zinc hydroxide, or by adding alkali to a titanium compound or an aluminum compound other than th~~ hydroxide or a mixture thereof for co-precipitation, f~ollowE~d by washing, molding and calcining, according to a u;~ual manner.
In a composite of a zinc oxide and a metal oxide selected from Either croup IIIb o~_- Group IVa or both, the mixing order of each components (inc:lusive of a hydroxide) is not limited. For instance, it may be prepared by mixing a mixture of a titanium compound and an aluminum compound with a zinc compound as described above, or by mixing a mixture of either a titaniiun comloound or an aluminum compound and a zinc compound with tree other non-mixed compound thereof.
Otherwise, a carrier having desired properties for the catalyst according to tile present invention may be prepared by only mixing a powder of a zinc oxide, a titanium oxide, an aluminum oxide, etc. i.n a prescribed amount.
A transition mf=t.al may be carr_.ied on the above-prepared carrier according to a conventional method such as an impregnation method and a co-precipitation method.
As an example, in a case carrying Ni as a transition metal on a carrier made of a zinc oxide alone, water is gradually added dropwise to a zinc oxide for water absorbing at the inside of the= zinc oxide. It is preferred that the water absorbing is concjucted until it is saturated at the inside of the zinc oxide. Next, the necessary Ni amount is calculated by the saturated water absorbing amount and the zinc oxide amount.
then, an aqueous Ni salt (e.g., a nitrate, an acetate, a chloride) solution which has been adjusted to an appropriate concentration based on the calculated Ni amount, is absorbed in 2'1 2'650 2 the zinc oxide until it is saturated, followed by washing, drying, molding, and c~alcining.
It is :similar in cases where two or more transition metals are carried on a composite as carrier. For instance, i) water is absorbed at the inside of the composite (preferably until it is sa.turated), ii) the necessary transition metal amounts (the i~otal amount of two transition metals) are calculated by the saturated water absorbing amount and the zinc oxide amount in the composite, iii) an aqueous transition metals solution which has been adjusted to an appropriate concentration based on the calculated transition metals amount, is absorbed until it i.s saturated, followed by washing, etc. as mentioned above.
When the catalyst according to the present invention is used to obtain carbon monoxide in the reduction of carbon dioxide by hydrogen, a suitable carbon monoxide production can be achieved, even though a sulfur compound, such as HZS, is present in a raw material gas, or, in a case using a composite of zinc oxide, titanium oxide, and aluminum oxide as a carrier, a great amount of CO i~~ present in the raw material gas.
In the reaction using a catalyst according to the present invention, it is preferred to be conducted at a temperature of about 400°C or more, more preferably at about 500 to 600°C under a pressure of about 20 kg/cmz or less, more preferably atmospheric: pressure to about 5 kg/cmz, and GHSV of about 1000 to 30000 h-1.
As discussed above, the catalyst according to the present invention carp provide the following effects:
(1) Even though a sulfur compound, such as HZS, is present in a raw material gas for obtaining carbon monoxide by reduction reaction of carbon dioxide by hydrogen, the catalyst according to the pre:~ent invention is not poisoned, then the catalytic life is prolonged.
(2) Since them final product obtained by the reduction reaction is not contaminated with HZS by the reduction of the catalyst, no HZ~~ removal treatment is required.
(3) In particular, in cases where a composite of zinc oxide, titanium oxide and aluminum oxide is used as a carrier, even though CO is contained in an amount similar to COZ in a raw material gas, them reduction reaction proceeds favorably with improved selectivity without accompanying any side reaction such as the poisoning of a catalyst, the deposition of carbon and the formation of a light hydrocarbon.
(4) Accordingly, by conducting the above-mentioned reduction reaction, carbon monoxide can be produced with a high degree of conversion and high selectivity. .
The catalyst according to the present invention is of great industrial value for obtaining an oxo gas and the like.
The present invE~ntion will be further described in the following examples, but. the present invention should not be construed as being limited thereto.
In the :following examples, each reaction product (gas) was analyzed by means of a gas chromatography equipped with a thermal conductive detector (TCD), by charging 60/80 mesh of an active carbon i~o a column (made of SUS) having I.D. (Inner Diameter) of 3 mm~ y: 2 m. HZS was detected by a gas indicator tube (Kitagawa type).
20 g of a carrier obtained b;y mixing 9.8 g of titanium oxide powder, 5.7 g o:E zinc oxide powder and 4.5 g of aluminum oxide powder was dipped in an aqueous solution of 9.91 g of nickel ( I I ) nitra to hexahydrate [ Ni ( NU3 ) Z ~ 6H20 ] in 20 ml of water for 1 hour. After removal of the residual solution, the resulting product was dried at 120°C for 12 hours and calcined at 600°C for 3 hours. Then, a catalyst having NiO: 12.4 wt$, ZnO: 21.2 wt~, and balance: TiOz and A1z03 was obtained.
8 ml of the catalyst thus obtained was charged in a cylindrical reaction tube having an inner diameter of 16 mm~
and 50 ml/min of HZ was passed thereto under normal pressure at 350°C for 6 hours.
Thereafter, using the catalyst, a reduction reaction of COZ by HZ was conducted with a mixed gas of Hz:COz ( 1 : 1 ) as a raw material gas under normal pressure at 600°C and GHSV = 3000h''.
The resu~~ts are shown in Table 1.
20 g of a carrier which was prepared in the same manner as in Example 1 was dipped in an aqueous solution of 9.88 g of 2~ 2650 2 cobalt ( I I ) nitrate hE~xahydrate [ Co ( N03 ) 2 ~ 6H20 ] dissolved in 20 ml of water. After removal of the residual solution, the resulting product was dried at 120°C' for 12 hours and calcined at 600°C for 3 ihours. Then, a catalyst having CoO: 12.7 wt~, Zn0:21.5 wt$, and balance: TiOz and A1203 was obtained.
Using the catalyst thus obtained, a reduction reaction was conducted in the name manner as in Example 1.
The results are shown in Table 1.
In an aqueous anunonium para-molybdate solution in which . 2 g of ammonium para-~molybdate tetrahydrate [ ( NH4 ) 6MO~OZ4 ~ 4Hz0 ]
was dissolved i.n 20 ml of water and aqueous ammonia was dropwise added thereto was dipped 20 g of a carrier which was prepared in the ;same manner as in Example 1 for 1 hour. After removal of the :residual solution, the resulting product was dried at 120°C to 12 hours and calcined at 600°C for 3 hours.
Then, a catalyst havi.n.g Mo03: 15 wt$, ZnO: 21.3 wt~, balance:
Ti02 and A1203 wa:~ obta.ined.
Using the catalyst thus obtained, a reduction reaction was conducted in the same manner as in Example 1.
The results arE~ shown in Table 1.
A catalyst having NiO: 19.1 wt$, ZnO: 70.0 wt~ was prepared in the same manner as in Example 1, except that 20 g of a carrier made of zin<~ oxide alone (a molded product of "G-72" produced by Girdles Co.) and an aqueous solution of 19.86 g of nickel ( I I ) nitrate hexahydrate [ Ni ( N03 ) Z ~ 6H20 ) dissolved in 20 ml of water were u.s~~d.
Using tlZe catalyst thus obtained, a reduction reaction was conducted in the same manner as in Example 1.
The results arE~ shown in Table 1.
A catalyst having NiO: 12.4 wt~ and balance: TiOz and A1203 was prepared in the same manner as in Example 1, except that 20 g of a carrier made from a mixture of 10 g of titanium oxide powder and 10 g of aluminum oxide powder was used.
Using the catalyst thus obtained, a reduction reaction was conducted in the same manner as in Example 1.
The results a:re shown in Table 1.
Ex.l Ex. 2 Ex. 3 Ex. 4 Comp. Ex. 1 Formed Gas Composition:
(Vol$) Hz 40.4 41.3 41.9 37.5 41.0 CO 21.0 20.2 18.5 22.0 20.8 COZ 38.5 38.4 39.6 39.3 38.1 CH4 0.1 0.1 0.0 1.2 0.1 Degree of Conversion: 35.0 34.0 32.0 36.6 34.9 ($) Selectivity: 99.5 99.5 100 94.8 99.5 ( Equilibrium Degree of Conversion: 385 38.5 38.5 38.5 38.5 ( In the results of Table 1, the degree of conversion and the selectivity are calculated by the following two equations, and the equilibrium degree of conversion means a theoretical degree of conversion.
(C'.Oz Mol. Number in .- (C02 Mol. Number Degree of Raw Material Gas) in Formed Gas) Conversion = ____._____.___________________________________ x 100 C0.> M~~1. Number in Raw Material Gas (CO Mol. Number - (CO Mol. Number in in Formed Gas) Raw Material Gas) Selectivity = _________.__________________________________x 100 ( ~ ) ( c~02 Mol . Number in _ ( C02 Mol . Number Raw Material Gas) in Formed Gas) A reduction rea~~tion was conducted in the same manner as in Example 1, except that a catalyst prepared in the same manner as in Example 4 was used and a mixed gas of Hz:COz (1:1) containing 200 p:pm of H;S was used as a raw material gas.
The resu:Lts are shown in Table 2.
Reaction Time 50 Hr 100 Hr 150 Hr Formed Gas Composition (Volt):
HZ 37.4 37.5 37.5 CO 21.9 22.0 22.0 COZ 39.5 39.5 39.5 CH4 1.2 1.1 1.1 Degree of Conver:;ion ( '~ ) : 36 . 5 36 . 5 36 . 5 Selectivity (~): 94.8 95.2 95.2 Outlet HZS Concentration (ppm): 0 0 0 2'1 2650 2 C:OMPARATIVE EXAMPLE 2 A reduction reaction was conducted in the same manner as in Example J., exc<~pt for using a catalyst prepared in the same manner a~~ in Comparative Example 1 and a mixed gas prepared in the same manner as in Example 5.
The results are shown in Table 3.
Reaction Time 50 Hr 100 Hr 150 Hr Formed Gas Composition (Vol$):
HZ 47,1 48.4 49.3 CO 8.5 3.7 0.8 COZ 44.4 47.9 49.9 CH4 0.0 0.0 0.0 Degree of Conversion (~~): 16.0 7.1 1.5 Selectivity ($). 100 100 100 Outlet HZS Concentration (ppm): 18 92 183 The results of Tables 1 to 3 support the following:
regardless of the presence of zinc oxide in a carrier of a catalyst, when a sulfur compound such as HzS was not present in a raw material c~as, a high degree of conversion was achieved.
However, when a sulfur ~~ompound, such as HZS, was present in a raw material gas, in cares using a catalyst containing no zinc oxide in a carrier, HZS~ was passed into a formed gas or the catalyst was poisoned. with a sulfur compound such as HZS, whereby the de~~ree of conversion was decreased and the catalytic life was shortened.
~1 2s5o 2 In cases using the catalysts according to the present invention, no HZS was ~~bserved in a formed gas and, since the catalytic life Haas prolonged, the catalysts were not poisoned.
C'.O.MPARATIVE EXAMPLE 3 8 ml of a comanercially available molybdenum disulfide was charged to a cylindrical reaction tube having an inner diameter of 16 mm~. LJsing this, a reduction reaction of COZ by HZ was conducted with a mixed gas of HZ:COZ (1:1) under normal pressure at 600°C and GHSV = 3000h-1. Then, a change of the degree of conversion and a change o:f the HZS concentration in a formed gas with the lapse of a reaction time were determined.
From the figure, it is apparent that when a metal sulfide is used as a catalyst, a sulfide as a catalytic component is reduced by hydrogen to form HZS even though no sulfur compound, such as HZS, is present in a raw material gas, the formed HZS is transferred to a formed gas, whereby the catalytic activity is decreased.
Using the catalyst prepared in the same manner as in Example 1, a reduction of COZ was conducted continuously in the same manner as in Example 1, except that a mixed gas of HZ
( 49 . 7 volt ) , CO ( 28 . 4 volt ) , COZ ( 21 . 8 volt ) and CH4 ( 0. 1 volt ) containing 200 ppm of HZS was used as a raw material gas.
The results with the lapse of 24 hours and the lapse of 200 hours are shown in.'rable 4.
20 g of a carrier which was prepared in the same manner as in Example 1 was dipped in an aqueous solution of 26.15 g of iron ( I I I ) nitrate nonahydrate [ Fe ( N03 ) 3 ~ 9H20 ] dissolved in 20 ml of water for 1 hour. after removal of the residual solution, the resulting product was dried at 120°C for 12 hours and calcined at 600°C for :3 hours. Then, a catalyst having Fe203:
20.5 wt~, ZnO: 21.2 wt~, and balance: Ti02 and A1203 was obtained.
Using the catalyst thus obtained, a reduction reaction was conducted in the same manner as in Example 6.
The resL~lts with the lapse of 24 hours and the lapse of 200 hours are shown in Table 4.
A reduction reaction was conducted in the same manner as in Example 6, except for using the catalyst which was prepared in the same rnanner as in Example 3.
The results with the lapse of 24 hours and the lapse of 200 hours are shown in Table 4.
TABLE
Example Examp le Examp le Reaction Time: 24 200 24 200 24 200 (Hr) Formed Gas Composition:
(Vol$) HZ 45.'7 46.0 46.1 46.5 44.8 44.7 CO 36.'7 35.7 36.4 35.1 37.1 37.2 COZ 17.:3 17.9 17.3 18.1 17.9 17.9 CH4 0.:3 0.4 0.2 0.3 0.2 0.2 Degree of Conversion: 27.2 24.5 26.9 23.4 25.8 26.0 ( Selectivity: 94.4 88.9 93.2 85.1 97.0 96.7 ($) C-Balance: 99.7 99.3 99.4 98.8 99.8 99.8 ( In Tab_Le 4, the degree of conversion and the selectivity were calculated by the same equations described earlier in Table 1. 'rhe C-balance is a mass balance of a raw material system and a formed material system, and the lower C-balance means the deposition of carbon on a catalyst.
As is apparent: from Table 4, in cases using a catalyst according to the present: invention, especially a catalyst using a composite of a. zinc oxide, a titanium oxide and an aluminum oxide as a carrier, even though a great amount of CO is present in a raw material ga:>, the degree of conversion and the selectivity are not decreased with the lapse of time, and the 2~1 2650 2 catalyst is not: poisoned with CO in the raw material gas, or the C-balance is not decreased.
Also, it is apparent that when a great amount of CO is present in a ~~aw material gas, it is preferred to use a catalyst which carries a molybdenum oxide on such a composite.
While the invention has been described in detail and with reference to spe~~ific embodiments thereof, it will be apparent to onf~ skill in the art that various changes and modifications can be made therein without departing from the spirit and scopE= thereof.
Claims (32)
1. A catalyst for the reduction of carbon dioxide comprising a transition metal on zinc oxide alone or on a composite containing zinc oxide and at least one metal oxide of a metal selected from the metals in Group IIIb and Group IVa in the Periodic Table.
2. A catalyst for the reduction of carbon dioxide as claimed in claim 1, wherein the metal oxide is selected from metal oxides of Al, Ga, Ti and Zr and composites thereof.
3. A catalyst for the reduction of carbon dioxide as claimed in claim 1 or 2, wherein the metal oxide or the composite thereof is used in an amount of 40 to 80 wt%
based on the total amount of the catalyst in terms of the metal oxide.
based on the total amount of the catalyst in terms of the metal oxide.
4. A catalyst for the reduction of carbon dioxide as claimed in any one of claims 1 to 3, wherein the transition metal is at least one metal selected from those in Group VIII and Group VI in the Periodic Table.
5. A catalyst for the reduction of carbon dioxide as claimed in any one of claims 1 to 3, wherein the transition metal is at least one metal selected from the group consisting of Ni, Fe, Co, Ru, Rh, Pt, Pd, Mo and W.
6. A catalyst for the reduction of carbon dioxide as claimed in any one of claims 1 to 5, wherein the transition metal is used in an amount of 5 to 20 wt% based on the total amount of the catalyst in terms of the metal oxide.
7. A catalyst for the reduction of carbon dioxide as claimed in any one of claims 1 to 6, wherein the zinc oxide is used in an amount of 20 to 100 wt% based on the total amount of the catalyst in terms of the metal oxide.
8. A catalyst for the reduction of carbon dioxide as claimed in claim 2, wherein the transition metal is on a composite of zinc oxide and titanium oxide.
9. A catalyst for the reduction of carbon dioxide as claimed in claim 2, wherein the transition metal is on a composite of zinc oxide and aluminum oxide.
10. A catalyst for the reduction of carbon dioxide as claimed in claim 2, wherein the transition metal is on a composite of zinc oxide, titanium oxide and aluminum oxide.
11. A method for reducing carbon dioxide by hydrogen in the presence of a catalyst where the reaction proceeds in the absence of an accompanying hydrocarbon forming side reaction, wherein said catalyst comprises a transition metal on a carrier comprising zinc oxide alone or on a carrier comprising zinc oxide and at least one metal oxide of a metal selected from metals in Group IIIb and IVa in the Periodic Table.
12. The method as claimed in claim 11, wherein the metal oxide is selected from the group consisting of a metal oxide of Al, Ga, Ti or Zr and a composite metal oxide of two or more metal oxides of Al, Ga, Ti and Zr.
13. The method as claimed in claim 11 or 12, wherein the transition metal is at least one metal selected from those in Group VIII and Group VIa in the Periodic Table.
14. The method as claimed in claim 11 or 12, wherein the transition metal is at least one metal selected from the group consisting of Ni, Fe, Co, Ru, Rh, Pt, Pd, Mo and W.
15. The method as claimed in any one of claims 11 to 14, wherein the transition metal is present in the catalyst in an amount of 5 to 20 wt % based on the total amount of the catalyst.
16. The method as claimed in any one of claims 11 to 15, wherein the zinc oxide is present in the catalyst in an amount of 20 to 100 wt % based on the total amount of the carrier.
17. The method as claimed in claim 11, wherein the catalyst comprises a transition metal on a carrier comprising zinc oxide and titanium oxide.
18. The method as claimed in claim 11, wherein the catalyst comprises a transition metal on a carrier comprising zinc oxide and aluminum oxide.
19. The method as claimed in claim 11, wherein the catalyst comprises a transition metal on a carrier comprising zinc oxide, titanium oxide and aluminum oxide.
20. The method as claimed in any one of claims 11 to 19, wherein the zinc oxide is present in the catalyst in an amount of 20 to 60 wt % based on the total amount of the carrier.
21. The method as claimed in claim 11, wherein the transition metal comprises molybdenum present as oxide, and the carrier comprises zinc oxide and aluminum oxide.
22. The method as claimed in claim 11, wherein the transition metal comprises nickel present as oxide, and the carrier comprises zinc oxide and aluminum oxide.
23. The method as claimed in claim 21, wherein molybdenum is present as oxide in the catalyst in an amount of 5 to 20 wt % based on the total amount of the catalyst.
24. The method as claimed in claim 21 or 23, wherein the zinc oxide is present in the catalyst in an amount of 20 to 60 wt % based on the total amount of the carrier.
25. The method as claimed in claim 22, wherein nickel is present as oxide in the catalyst in an amount of 5 to 20 wt % based on the total amount of the catalyst.
26. The method as claimed in claim 22 or 25, wherein the zinc oxide is present in the catalyst in an amount of 20 to 60 wt % based on the total amount of the carrier.
27. A method for reducing carbon dioxide by hydrogen in the presence of a catalyst, wherein said catalyst comprises molybdenum present as oxide on a carrier comprising zinc oxide and aluminum oxide.
28. A method for reducing carbon dioxide by hydrogen in the presence of a catalyst, wherein said catalyst comprises nickel present as oxide on a carrier comprising zinc oxide and aluminum oxide.
29. The method as claimed in claim 27, wherein molybdenum is present as oxide in the catalyst in an amount of 5 to 20 wt % based on the total amount of the catalyst.
30. The method as claimed in claim 27 or 29, wherein the zinc oxide is present in the catalyst in an amount of 20 to 60 wt % based on the total amount of the carrier.
31. The method as claimed in claim 28, wherein nickel is present as oxide in the catalyst in an amount of 5 to 20 wt % based on the total amount of the catalyst.
32. The method as claimed in claim 28 or 31, wherein the zinc oxide is present in the catalyst in an amount of 20 to 60 wt % based on the total amount of the carrier.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JPHEI.5-180780 | 1993-06-25 | ||
| JP18078093 | 1993-06-25 | ||
| JP5261904A JP2847018B2 (en) | 1993-06-25 | 1993-09-23 | Carbon dioxide reduction reaction catalyst |
| JPHEI.5-261904 | 1993-09-23 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2126502A1 CA2126502A1 (en) | 1994-12-26 |
| CA2126502C true CA2126502C (en) | 2003-12-30 |
Family
ID=26500177
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002126502A Expired - Fee Related CA2126502C (en) | 1993-06-25 | 1994-06-22 | Catalyst for reduction of carbon dioxide |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP2847018B2 (en) |
| CA (1) | CA2126502C (en) |
| DE (1) | DE4422227C2 (en) |
| GB (1) | GB2279583B (en) |
Families Citing this family (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2806073B1 (en) * | 2000-03-07 | 2002-06-07 | Air Liquide | PROCESS FOR PRODUCING CARBON MONOXIDE BY REVERSE RETROCONVERSION WITH AN ADAPTED CATALYST |
| AU2003299027A1 (en) * | 2002-09-23 | 2004-04-08 | Shell Internationale Research Maatschappij B.V. | Catalyst particles and its use in desulphurisation |
| US20090062110A1 (en) | 2006-02-08 | 2009-03-05 | Sumitomo Chemical Company Limited | Metal complex and use thereof |
| CN101678329B (en) | 2007-04-27 | 2013-09-18 | 沙特基础工业公司 | Catalytic hydrogenation of carbon dioxide into syngas mixture |
| EA016496B9 (en) | 2007-06-25 | 2012-07-30 | Сауди Бейсик Индастриз Корпорейшн | Process of making a syngas mixture |
| JP5533862B2 (en) * | 2009-05-15 | 2014-06-25 | 富士通株式会社 | Gas generating apparatus and gas generating method |
| WO2010131363A1 (en) * | 2009-05-15 | 2010-11-18 | 富士通株式会社 | Carbon monoxide gas generator and method of generating carbon monoxide gas |
| GB2546929B (en) | 2010-09-13 | 2018-04-04 | Lummus Technology Inc | Low temperature sulfur tolerant and sulfur removal with concomitant synthesis gas conditioning |
| WO2012153762A1 (en) * | 2011-05-11 | 2012-11-15 | 株式会社村田製作所 | Reverse shift reaction catalyst, and method for producing synthetic gas using same |
| US8962702B2 (en) | 2011-12-08 | 2015-02-24 | Saudi Basic Industries Corporation | Mixed oxide based catalyst for the conversion of carbon dioxide to syngas and method of preparation and use |
| US8551434B1 (en) | 2012-06-29 | 2013-10-08 | Saudi Basic Industries Corporation | Method of forming a syngas mixture |
| EP3063113A1 (en) | 2013-10-29 | 2016-09-07 | Saudi Basic Industries Corporation | Method for carbon dioxide hydrogenation of syngas and the integration of the process with syngas conversion processes |
| CN105899648A (en) | 2014-01-06 | 2016-08-24 | 沙特基础工业公司 | Method for carbon dioxide hydrogenation of syngas |
| WO2015153610A1 (en) | 2014-04-03 | 2015-10-08 | Saudi Basic Industries Corporation | Process for converting of methane stream reforming syngas with co2 |
| RU2632701C1 (en) * | 2016-06-21 | 2017-10-09 | ФЕДЕРАЛЬНОЕ ГОСУДАРСТВЕННОЕ БЮДЖЕТНОЕ УЧРЕЖДЕНИЕ НАУКИ ИНСТИТУТ ОРГАНИЧЕСКОЙ ХИМИИ им. Н.Д. ЗЕЛИНСКОГО РОССИЙСКОЙ АКАДЕМИИ НАУК (ИОХ РАН) | Method of producing synthesis gas from co2 |
| EP3804851A4 (en) * | 2018-05-29 | 2022-03-02 | Sekisui Chemical Co., Ltd. | Catalyst, method for reducing carbon dioxide, and apparatus for reducing carbon dioxide |
| CN109647373B (en) * | 2018-11-28 | 2021-03-23 | 天津大学 | Black indium oxide ultrathin nanosheet and preparation method and photo-thermal catalysis application thereof |
| US20220111354A1 (en) | 2018-11-29 | 2022-04-14 | Jawaharlal Nehru Centre For Advanced Scientific Research | Catalyst and process of preparing the same |
| CN115515712A (en) | 2020-05-04 | 2022-12-23 | 英飞纳姆科技有限责任公司 | Reverse water gas shift catalytic reactor system |
| CA3215266A1 (en) | 2020-05-04 | 2021-11-11 | Infinium Technology, Llc | Process for capture of carbon dioxide from air and the direct conversion of carbon dioxide into fuels and chemicals |
| US11498886B2 (en) | 2020-05-04 | 2022-11-15 | Infinium Technology, Llc | Catalysts and processes for the direct production of liquid fuels from carbon dioxide and hydrogen |
| CA3204926A1 (en) | 2020-05-04 | 2021-11-11 | Infinium Technology, Llc | Process for conversion of carbon dioxide and power into fuels and chemicals |
| US12104125B2 (en) | 2021-02-05 | 2024-10-01 | Infinium Technology, Llc | Efficient 2-step process for the direct production of liquid fuels from carbon dioxide and hydrogen |
| JPWO2022210832A1 (en) * | 2021-03-31 | 2022-10-06 | ||
| US20230150823A1 (en) | 2021-11-16 | 2023-05-18 | Dennis Schuetzle | CO2 hydrogenation catalysts for the commercial production of syngas |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE963980C (en) * | 1953-05-19 | 1957-05-16 | Standard Oil Dev Co | Process for the production of highly active reforming catalysts |
| US2846365A (en) * | 1954-12-29 | 1958-08-05 | Exxon Research Engineering Co | Hydroforming catalyst containing a group vi metal oxide supported on a zinc-zirconium aluminate spinel |
| FR1340206A (en) * | 1962-06-29 | 1963-10-18 | Azote Office Nat Ind | Industrial gas and vapor desulfurization catalysts |
| US3798156A (en) * | 1971-09-22 | 1974-03-19 | Standard Oil Co | Hydroprocessing catalyst and process |
| DE2657598A1 (en) * | 1976-12-18 | 1978-06-22 | Krupp Koppers Gmbh | METHOD FOR PRODUCING A CARBON-MONOXY-THICK GAS |
| FR2441420A1 (en) * | 1978-11-17 | 1980-06-13 | Catalyse Soc Prod Francais | CATALYST CONTAINING COPPER OXIDE, ZINC OXIDE AND RARE EARTH, ITS PREPARATION AND ITS USE IN CARBON MONOXIDE CONVERSION REACTIONS |
| US4389305A (en) * | 1980-02-18 | 1983-06-21 | Phillips Petroleum Company | Catalytic hydrodenitrogenation of organic compounds employing promoted zinc titanate |
| DE3610698A1 (en) * | 1986-03-29 | 1987-10-01 | Henkel Kgaa | CATALYST AND METHOD FOR THE CATALYTIC HYDRATION OF FATTY ACID METHYL ESTERS IN THE FIXED BED |
| JP2738945B2 (en) * | 1987-08-03 | 1998-04-08 | イーストマン ケミカル カンパニー | Low pressure catalytic hydrogenation of carbonyl-containing compounds and catalyst for the hydrogenation |
| GB9225372D0 (en) * | 1992-12-04 | 1993-01-27 | British Petroleum Co Plc | Oxide compositions |
-
1993
- 1993-09-23 JP JP5261904A patent/JP2847018B2/en not_active Expired - Fee Related
-
1994
- 1994-06-22 CA CA002126502A patent/CA2126502C/en not_active Expired - Fee Related
- 1994-06-23 GB GB9412673A patent/GB2279583B/en not_active Expired - Fee Related
- 1994-06-24 DE DE4422227A patent/DE4422227C2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| GB2279583A (en) | 1995-01-11 |
| DE4422227A1 (en) | 1995-01-05 |
| GB2279583B (en) | 1997-09-24 |
| CA2126502A1 (en) | 1994-12-26 |
| JP2847018B2 (en) | 1999-01-13 |
| DE4422227C2 (en) | 2003-10-02 |
| GB9412673D0 (en) | 1994-08-10 |
| JPH0768171A (en) | 1995-03-14 |
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